Anthraquinone vat dyes.



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MAX HENRY ISLER, OF MANNHEIM, GERMANY, ASSIGNOR'TO BADISCHE ANILIN & -SODA FABRIK, OF LUDWIGSHAFEN-ON-THE-RHINE, GERMANY, A CORPORATION.

AN THRAQUIN ON E VAT DYES.

No Drawing.

To all whom it may concern:

Be it lmown that I, MAX citizen of the Swiss Republic, residing at Mannheim, Germany, have invented new and useful Improvements in Anthraquinone Vat Dyes, of which the following is a specification.

I have discovered new vat coloring matters of the anthraquinone series which are anthraquinone-diaryl-dithiazoles and possess a constitution corre ponding to the formula s v s R C/ \A/ \C R in which A represents the anthraquinone residue and R represents an aryl residue, including those of the benzene, naphthalene and anthraquinone series. I can obtain my new compounds by treating 1.5-dimercapto- 2.6 diam'inoanthraquinone, or 1.8-dimercapto 2.7 diamino anthraquinone, with an aryl aldehyde or with a corresponding omegadihalogen-methyl compound, or equivalent the reaction be carried out under sufiiciently mild conditions, an intermediate product is produced which is probably a dihydro-dithia'zole, and is convertible, by treatment with an oxidizing agent, or even by standing with concentrated sulfuric acid, into the anthraquinone-diphenyl-dithiazole, or this latter can be directly produced if the reaction is allowed to continue for some HENRY ISLER,

time at a higher temperature, or in the presence of an oxidizing agent, either organic or inorganic. Instead of employing either of the aforesaid dimercapto-diamino-anthraquinones, .the corresponding dihalogendiam1no-anthraquinone can sometimes be employed, if the condensation be carried out in the presence of a body (such, for instance, as a polysulfid)- which is capable of replacing the halogen atom by the S, or the SH, residue.

My new compounds consist, when dry, of yellow powders which are insoluble in dis lute acids and alkalis, but are'soluble in concentrated sulfuric acidgiving reddish yellow solutions, and dye cotton, from a hydrosulfite vat, yellow to yellow-orange shades.

Specification of Letters Patent. Application filed October 1, 1912. Serial No. 723,307.

portion of the isolated Patented Mar. 17,1914.

The following examples will serve to illustrate further the nature of my invention and how it canbe carried into practical eflect, butthe inventionis not confined to these examples. The parts are by weight.

Example 1: Boil together, in a reflux apparatus, 50 parts of 2.6-diamino-anthraquinone-1.5-dimercaptan, dehyde, and 750 parts of pyridin, or of nitrobenzene, until a test portion of the product dissolves in concentrated sulfuric acid, forming a yellow solution. Filter 0H the reaction product when cold and wash it with cold nitrobenzene, whereupon a yellow vat dye is obtained which is insoluble in dilute acids and alkalis and in the usual solvents when cold. It can be obtained in the 100 parts of benzal- .pure state by recrystallization from, for instance, boiling nitrobenzene. In concentrated surfuric acid it yields a reddish yellow solution and, after being precipitated by means of water and treated with sodium hypochlorite, it yields a paste which, from a hydrosulfite vat, dyes yellow shades. In

this example, instead of benzaldehyde, ben- Zal chlorid, benzotrichl'orid, or benzoyl chlorid, can be employed. The pure vat coloringmatter obtainable according to this example, when analyzed, yields results which point to its possessing a constitution corresponding to the formula CGH5JJ ISI Found: Theory: N 5.66% 5.89% 5.9% S ..13.59% 13.63% 13.5%

Example 2: Condense together, at a temperature of from 50 to 0., 50 parts of 2.6-diamino-santhraquinona1.5-dimercaptan, from 2501 to 500 parts of pyridin, and 40 parts of benzaldehyde. The reaction proceeds very easily and is stopped when a test product yields a and not a yellow solution,

green. solution,

being dissolved in concenimmediately on trated sulfuric acid. The brown reaction product yields a green solution in sulfuric acid, which solution however very rapidly becomes yellow, and the whole of this brown reaction product .can be converted into the anthraquinone diphenyl-dithiazole then pouring into water and filtering oil and washing the coloring matter.

Example 3: Heat together, in a closed vessel, for a few hours, at from 120 to 130 C., 50 parts of 2.6-diamino-l.5-dichlor-anthraquinone (preferablyin the form of a finely divided paste), from 500 to 1,000 parts of sodium polysulfid .solution' (obtained from 250 parts of crystallized sodium sulfid, 400

parts of sulfur and 400 parts of water,

and 100 parts of benzalparts of alcohol) dehyde. Isolate the coloring matter in the a usual way. If desired, it can be purified by treating it for a short time W1th sodium hypochlorite, or by recrystallization from nitrobenzene. It is identical with the product of the foregoing Example 2.

In a similar manner to that described in the foregoing examples, coloring matter can be obtained. from 2.7-diamino-anthraquinone- 1.8 dimercaptan. Further, similar products can be obtained by condensing anthraquinone-aldehyde or omega-dihalogen- Q-methyl-anthraquinone or anthraquinonecarboxylic-acid chlorid with either of the aforesaid dimercapto diamino anthraquinones.

, Now what I claim is 1. The new vat dyes of the anthraquinone iseries being anthraquinone-di-aryl-dithiazoles, which possess a constitution corresponding to the formula in which A represents an anthraquinone residue and R an aryl residue, which new vat dyes consist, when dry, of yellow powders which are insoluble indiiute acids and alkalis, but are soluble in cor. =entrated sulfuric acid giving reddish yellow solutions, and dye cotton, from a hydro su lfite vat, yellow to yellow-orange shades.

2. The new coloring matter of the anthra-' quinone series which is 1.2.5.6-anthraquinone-diphenyl-dithiazole', which possesses a constitution corresponding to the formula s c-can s witnesses.

MAX HENRY ISLER. Witnesses: I V I J Ante. LLoYD,

Jo'snrir HE FFER. 

